Magnetic glass and preparation method and application thereof

Abstract

The invention relates to the technical field of functional glass materials and composite manufacturing, in particular to magnetic glass as well as a preparation method and application thereof. The preparation method of the magnetic glass comprises the following steps: S1, glass pretreatment; s2, sealing the bottom of the glass; s3, substrate pretreatment; s4, electrolyte preparation and electro-deposition, wherein electrolyte comprises magnetic metal salt, a complexing agent and a dispersing agent, and electro-deposition is conducted through a three-electrode system; s5, post-treatment: carrying out heat treatment and surface modification; s6, bonding a magnetic film; and S7, an MI process is carried out, wherein a texture mold is adopted, and a micro-nano imprinting technology is adopted. On the basis of combination of electro-deposition and an MI process, the magnetic glass with a large area and a uniform magnetic adsorption function is prepared, and meanwhile it is ensured that the sealing performance, the heat preservation performance and the structural strength of a door body are not affected.

Description

Technical Field

[0001] This invention relates to the field of functional glass materials and composite manufacturing technology, and in particular to a magnetic glass, its preparation method and application. Background Technology

[0002] In modern home life, home appliances not only need to meet basic functional requirements but also need to cater to users' needs for personalized decoration and convenience. Traditional glass for home appliances, with its smooth surface and good visual effect, is widely used on the doors of various home appliances, such as refrigerators and ovens. However, this smooth glass surface has obvious limitations. Because it lacks magnetic adsorption capabilities, users cannot directly attach magnetic items such as refrigerator magnets to the glass surface. This greatly limits users' needs for personalized decoration of home appliances and cannot meet users' needs for convenient operations using magnetic adsorption functions, such as sticking notes or displaying photos.

[0003] To address the issue of traditional glass panels for home appliances being unable to attract magnetic items, some technological attempts have been made. Some appliance glass panels utilize magnetic strips along the door edge or in specific areas to achieve this attraction. However, this solution has several drawbacks: firstly, the magnetic strips are only placed along the door edge or in specific areas, resulting in a very small area for magnetic attraction, limiting the range of items users can attach and failing to fully meet the needs for personalized decoration and convenience; secondly, the magnetic strips detract from the overall aesthetics of the door, contradicting the original design philosophy of simplicity and beauty pursued in appliance glass.

[0004] Furthermore, the method of fixing the magnetic strip is also a significant issue. During installation, the door's sealing structure may be damaged, leading to a decrease in its airtightness. For appliances that require stable internal temperatures, such as refrigerators and freezers, reduced airtightness allows external heat to enter more easily, increasing energy consumption and raising user costs. This also contradicts current trends towards energy conservation and environmental protection.

[0005] In summary, existing technologies for achieving magnetic adsorption on the glass surfaces of household appliances have many shortcomings, failing to simultaneously meet users' requirements for large-area adsorption, aesthetics, sealing, insulation, and structural strength. Therefore, an innovative solution is urgently needed that can achieve large-area, uniform magnetic adsorption on the glass surfaces of household appliances, solving the technical problems of traditional glass surfaces' inability to stably adsorb metal objects and poor functional expandability, while ensuring that the sealing, insulation, and structural strength of the door are not affected. Summary of the Invention

[0006] In order to solve the above-mentioned technical problems in the prior art, the present invention provides a magnetic glass, its preparation method and application.

[0007] The technical solution of the present invention to solve the above-mentioned technical problems is as follows: The first aspect of this invention is to provide a method for preparing magnetically pleasing glass, comprising the following steps: S1. Glass pretreatment; S2, Glass-sealed bottom; S3, Substrate pretreatment; S4. Electrolyte preparation and electrodeposition: The electrolyte includes magnetic metal salt, complexing agent and dispersant. Electrodeposition is performed on the substrate using a three-electrode system to obtain a magnetic thin film. S5. Post-processing: Heat treatment and surface modification of the magnetic thin film; S6. Adhede the magnetic film: Adhere the magnetic film to the glass backing; S7 and MI processes: using textured molds and micro-nano imprinting technology.

[0008] The method for preparing magnetic glass provided by this invention is based on the combination of electrodeposition and MI (multilayer interconnect) process to prepare magnetic glass with large area and uniform magnetic adsorption function, while ensuring that the sealing, heat preservation and structural strength of the door are not affected.

[0009] Based on the above technical solution, the present invention can also be improved as follows: Furthermore, in step S6, the magnetic thin film is a CoPtMo ternary alloy magnetic thin film.

[0010] Further, in step S4, the electrolyte includes: cobalt sulfate (CoSO4), chloroplatinic acid (H2PtCl6), and sodium molybdate (Na2MoO4), and the molar ratio of cobalt sulfate (CoSO4), chloroplatinic acid (H2PtCl6), and sodium molybdate (Na2MoO4) is (2.5~5):1:(0.1~2).

[0011] Furthermore, the electrolyte also includes citric acid and polyethylene glycol, wherein the concentration of citric acid is 0.1–0.5 mol / L and the concentration of polyethylene glycol is 0.01–0.1 g / L.

[0012] The beneficial effect of adopting the above-mentioned further technical solution is that by adding citric acid as a complexing agent, Mo ions are stabilized.

[0013] Furthermore, in the three-electrode system, the working electrode is made of copper foil, which has good conductivity and is suitable for thin film adhesion; the reference electrode is made of silver / silver chloride electrode (Ag / AgCl); and the auxiliary electrode is made of inert material, preferably platinum sheet.

[0014] Furthermore, in step S4, the pH value of the electrolyte is 4-6; and the current density for electrodeposition is controlled to be 1-100 mA / cm². 2 The temperature is 20–60℃; the thickness of the electrodeposited film is controlled to be 50–5000 nm.

[0015] The beneficial effects of adopting the above-mentioned further technical solutions are as follows: the film thickness needs to be controlled. If the film thickness is too thin, the magnetic properties will deteriorate, the surface roughness will increase, and the process stability will decrease. If the film thickness is too thick, the magnetic properties will degrade, the internal stress will increase, and the process cost will increase.

[0016] Furthermore, in step S5, the heat treatment specifically includes the following processes: (1) Annealing heat treatment: control the annealing heat treatment temperature to be 400-800℃, the annealing heat treatment time to be 1-3h, and the heating rate to be 1-10℃ / min; (2) Atmosphere-controlled heat treatment: Heat treatment is carried out in an inert and / or reducing atmosphere, with the heat treatment temperature controlled at 400-800℃, the time at 0.5-4h, and the heating rate at 1-10℃ / min.

[0017] The beneficial effects of adopting the above-mentioned further technical solutions are as follows: high-temperature annealing eliminates internal stress in the film, improves crystallinity, promotes grain growth and composition homogenization, and promotes the phase transition from Al to L10 in the CoPtMo magnetic film, thereby enhancing vertical coercivity; heat treatment in a specific atmosphere prevents oxidation of the CoPtMo magnetic film, optimizes the film composition, removes the surface oxide layer, and improves interface quality.

[0018] Furthermore, the atmosphere consists of 5%–10% H2 and 90%–95% Ar by volume, and the gas flow rate is 50–200 mL / min.

[0019] Further, in step S1, the glass pretreatment includes glass faceting and glass cleaning; the glass faceting is done by using a tin lamp to face the glass with the air side facing upwards; the glass cleaning is done by placing the glass with the air side facing upwards in a cleaning machine for cleaning; in step S2, a screen printing process is used to seal the air side of the glass, followed by thermal curing; the screen printing mesh count is 100 or 200, the thermal curing temperature is 180℃, and the thermal curing time is 6–10 min; in step S3, the substrate is selected from a metal substrate, a semiconductor substrate, or a flexible substrate; the substrate pretreatment involves chemical etching, plasma treatment, or ion implantation; in step S5, the surface modification involves depositing SiO2 or Al2O3 on the surface of the magnetic thin film using chemical plating or physical vapor deposition; in step S6, a shadowless adhesive is used to bond the magnetic thin film using an imprinting device, controlling the imprinting device speed to be 3–5 m / min and the energy to be 1000–2000 mJ / cm². 2 .

[0020] Furthermore, the flexible substrate is polyimide (PI).

[0021] The beneficial effects of adopting the above-mentioned further technical solutions are as follows: Active groups (such as -OH, -COOH) are introduced by plasma treatment of the substrate, and N is introduced by ion implantation. + B + This improves the bonding strength between the film and the substrate; surface modification involves depositing a protective layer on the film surface to prevent oxidation and corrosion.

[0022] Texture molds refer to transfer molds used in glass products, which can transfer the texture pattern on the film onto the glass through the MT process.

[0023] Furthermore, in step S7, ultraviolet embossing is adopted: an ultraviolet curing process is introduced during the embossing process, and a low-viscosity polymer (such as resin, UV-curing adhesive, etc.) that is sensitive to ultraviolet light is used as the embossing adhesive, and the mold is removed after curing.

[0024] The beneficial effect of adopting the above-mentioned further technical solution is that different textures are imprinted, which plays a decorative and aesthetic role.

[0025] A second aspect of the present invention is to provide a magnetically absorbing glass, which is prepared using the preparation method provided in the first aspect of the present invention.

[0026] Another aspect of the present invention is to provide the application of the magnetic glass provided in the second aspect of the present invention in the fields of home appliance glass panels and smart interactive terminals.

[0027] Compared with the prior art, the present invention has the following technical effects: The method for preparing magnetic glass provided by this invention is based on the combination of electrodeposition and MI (multilayer interconnect) process to prepare magnetic glass with large area and uniform magnetic adsorption function, while ensuring that the sealing, heat preservation and structural strength of the door are not affected.

[0028] Electrodeposition is performed using a three-electrode system, which consists of a working electrode (copper foil, used for depositing magnetic thin films), a counter electrode (anode, selected as a platinum sheet, providing an electron transfer path), and a reference electrode (silver / silver chloride electrode, used for precise control of the working electrode potential). Precise potential control is achieved by using the potential difference between the reference electrode and the working electrode to accurately adjust the deposition potential, avoiding potential fluctuations caused by counter electrode polarization in traditional two-electrode systems. This optimizes the thin film composition and structure. In the preparation of CoPtMo magnetic thin films, the three-electrode system can stably control the Mo deposition rate, achieving a balance between performance and cost. Current efficiency is optimized because the three-electrode system allows for independent adjustment of the current distribution between the working electrode and the counter electrode, reducing the impact of side reactions (such as hydrogen evolution) on deposition efficiency. Detailed Implementation

[0029] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. Although the description of the present invention is presented in conjunction with preferred embodiments, this does not mean that the features of the invention are limited to this embodiment. On the contrary, the purpose of describing the invention in conjunction with embodiments is to cover other options or modifications that may be derived based on the claims of the present invention. To provide a deep understanding of the invention, many specific details will be included in the following description. The invention may also be implemented without using these details. Furthermore, to avoid confusion or obscuring the focus of the invention, some specific details will be omitted in the description. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of the present invention can be combined with each other.

[0030] Example 1 The method for preparing magnetic glass includes the following steps: S1. Glass pretreatment: Separate the glass facets with the air side facing up using a tin lamp; when the cleaning machine temperature reaches above 56℃, keep the air side of the glass facing up and place the glass in the cleaning machine for cleaning. S2. Glass back sealing: The back is sealed by screen printing on the air surface of the glass, and then heat-cured; the screen printing mesh number is 100 mesh, the heat curing temperature is 180℃, and the heat curing time is 10min. S3. Substrate pretreatment: The substrate is polyimide, which is subjected to plasma treatment; S4. Electrolyte Preparation and Electrodeposition: Electrolyte composition: Cobalt sulfate (CoSO4) 2.5 mol / L, chloroplatinic acid (H2PtCl6) 0.5 mol / L, sodium molybdate (Na2MoO4) 0.05 mol / L, citric acid 0.1 mol / L, polyethylene glycol 0.01 g / L; pH of the electrolyte is 6; a three-electrode system is used for electrodeposition, with copper foil as the working electrode; a silver / silver chloride electrode as the reference electrode; and a platinum sheet as the auxiliary electrode; the electrodeposition current density is controlled at 60 mA / cm². 2 The temperature was 30℃; the thickness of the electrodeposited film was controlled to be 600nm to obtain a CoPtMo ternary alloy magnetic film. S5. Post-treatment: Heat treatment and surface modification; Heat treatment was carried out in a magnetic material experimental furnace. During the heat treatment process, the annealing heat treatment temperature was controlled at 400℃, the annealing heat treatment time was 1h, and the heating rate was 5℃ / min; then, atmosphere-controlled heat treatment was carried out. The atmosphere for atmosphere-controlled heat treatment was 5% H2 and 95% Ar by volume. The atmosphere-controlled heat treatment temperature was 400℃, the time was 0.5h, and the heating rate was 3℃ / min. S6. Bonding Magnetic Films: Using shadowless adhesive, CoPtMo ternary alloy magnetic films are bonded via an imprinting device. The imprinting speed is controlled at 3 m / min, and the energy is 1000 mJ / cm². 2 ; S7 and MI processes: using textured molds and micro-nano imprinting technology.

[0031] Example 2 S1. Glass pretreatment: Separate the glass facets with the air side facing up using a tin lamp; when the cleaning machine temperature reaches above 56℃, keep the air side of the glass facing up and place the glass in the cleaning machine for cleaning. S2. Glass back sealing: The back is sealed by screen printing on the air surface of the glass, and then heat-cured; the screen printing mesh number is 100 mesh, the heat curing temperature is 180℃, and the heat curing time is 10min. S3. Substrate pretreatment: The substrate is polyimide, which is subjected to plasma treatment; S4. Electrolyte preparation and electrodeposition: Electrolyte composition: cobalt sulfate (CoSO4) 2.5 mol / L, chloroplatinic acid (H2PtCl6) 0.5 mol / L, sodium molybdate (Na2MoO4) 0.05 mol / L, citric acid 0.15 mol / L, polyethylene glycol 0.02 g / L; pH of the electrolyte was 6; electrodeposition was performed using the same three-electrode system as in Example 1; the electrodeposition current density was controlled at 50 mA / cm², the temperature at 35℃, and the film thickness at 800 nm to obtain a CoPtMo ternary alloy magnetic film; S5. Post-treatment: Heat treatment and surface modification; the treatment was carried out in a magnetic materials experimental furnace. During the heat treatment, the annealing heat treatment temperature was controlled at 450℃, the annealing heat treatment time was 2h, and the heating rate was 1℃ / min; then, atmosphere-controlled heat treatment was carried out. The atmosphere for atmosphere-controlled heat treatment was 5% H2 and 95% Ar by volume. The heat treatment temperature for atmosphere-controlled heat treatment was 420℃, the time was 1h, and the heating rate was 3℃ / min. S6. Bonding magnetic film: Compared with Example 1, the printing speed of the shadowless adhesive in this example is reduced to 2m / min, and the energy is 1200mj / cm². S7 and MI processes: using textured molds and micro-nano imprinting technology.

[0032] Example 3 S1. Glass pretreatment: Separate the glass facets with the air side facing up using a tin lamp; when the cleaning machine temperature reaches above 56℃, keep the air side of the glass facing up and place the glass in the cleaning machine for cleaning. S2. Glass back sealing: The back is sealed by screen printing on the air surface of the glass, and then heat-cured; the screen printing mesh number is 100 mesh, the heat curing temperature is 180℃, and the heat curing time is 10min. S3. Substrate pretreatment: The substrate is polyimide, which is subjected to plasma treatment; S4. Electrolyte preparation and electrodeposition: Electrolyte composition: cobalt sulfate (CoSO4) 3 mol / L, chloroplatinic acid (H2PtCl6) 0.6 mol / L, sodium molybdate (Na2MoO4) 1 mol / L, citric acid 0.18 mol / L, polyethylene glycol 0.015 g / L; pH of the electrolyte is 4; the same electrodeposition system as in Example 1 is used, and the electrodeposition parameters are: current density 50 mA / cm², temperature 35℃, and film thickness 400 nm.

[0033] S5. Post-treatment: Annealing heat treatment: temperature 600℃, time 0.5 hours, heating rate 5℃ / min; Atmosphere control heat treatment atmosphere is 5%H2 and 95%Ar, temperature 800℃, time 3 hours, heating rate 10℃ / min. S6. Bonding magnetic films: Low-temperature curing shadowless adhesive (curing temperature ≤80℃), imprinting speed 4m / min, energy 800mj / cm².

[0034] S7 and MI processes: using textured molds and micro-nano imprinting technology.

[0035] Example 4 S1. Glass pretreatment: Separate the glass facets with the air side facing up using a tin lamp; when the cleaning machine temperature reaches above 56℃, keep the air side of the glass facing up and place the glass in the cleaning machine for cleaning. S2. Glass back sealing: The back is sealed by screen printing on the air surface of the glass, and then heat-cured; the screen printing mesh number is 100 mesh, the heat curing temperature is 180℃, and the heat curing time is 10min. S3. Substrate pretreatment: The substrate is polyimide, which is subjected to plasma treatment; S4. Electrolyte Preparation and Electrodeposition: Electrolyte composition: cobalt sulfate (CoSO4) 5 mol / L, chloroplatinic acid (H2PtCl6) 2 mol / L, sodium molybdate (Na2MoO4) 1 mol / L, citric acid 0.2 mol / L, polyethylene glycol 0.03 g / L, pH value of electrolyte 5; electrodeposition was performed using the same three-electrode system as in Example 1; the electrodeposition current density was controlled at 60 mA / cm². 2 The temperature was 30℃; the film thickness was 300nm. S5. Post-treatment: Annealing heat treatment at 500℃ for 2 hours at a heating rate of 1℃ / min. Atmosphere-controlled heat treatment was performed in an atmosphere of 10% H2 and 90% Ar at a temperature of 500℃ for 2 hours at a heating rate of 8℃ / min. S6. Bonding magnetic films: using optical-grade shadowless adhesive, imprinting speed 1m / min, energy 1500mj / cm²; S7 and MI processes: using textured molds and micro-nano imprinting technology.

[0036] Comparative Example 1 Compared with Example 1, the difference in this comparative example is that the atmosphere-controlled heat treatment step is not performed in step S5. The rest is the same as in Example 1, and will not be repeated here.

[0037] Comparative Example 2 Compared with Example 1, the difference in this comparative example is that the electrolyte in step S4 does not contain chloroplatinic acid, while the rest is the same as in Example 1, and will not be repeated here.

[0038] The following performance tests were performed on the magnetic glass of the embodiments and comparative examples: ① Boiling water test: Place the sample in boiling water at 100℃ and boil for 2 hours. The coating surface should not have any swelling, peeling, flaking, discoloration, or watermarks. The front of the product should not have concentrated or dense pinholes or bubbles, watermarks, or color changes. It is considered qualified. ② Hardness: Use an H pencil according to the requirements of the standard GB / T 6739-2006 "Determination of Hardness of Paint Film by Pencil Method". The highest hardness level of the paint film without scratches is 5H, which is considered qualified. ③ Acid and alkali resistance: Drop 5% H2SO4 solution and 5% NaOH solution on the surface of the sample coating respectively for a spot test. Cover the spot area with a transparent cup for 24 hours, then wash with water and air dry naturally for 1 hour, and visually observe. If there is no trace at the spot, it is considered qualified. ④ Stain resistance: Drop pollutants on the surface of the sample. The pollution area of each pollutant should be no less than 15 cm 2 ~20 cm 2 , cover it with a glass plate and keep it at a constant temperature of 30℃ for 24 hours. After wiping, if there is no change in color or gloss on the surface of the coating and there is no phenomenon such as swelling or peeling of the surface coating, it is considered qualified. ⑤ Moisture resistance: Place the sample in a constant temperature and humidity box at a temperature of 65℃±2℃ and an air relative humidity of (93±3)% for 168 h. If there is no change on both the front and back sides of the sample after testing, it is considered qualified.

[0039] The performance test results of each example and comparative example are shown in Table 1.

[0040] Table 1 Performance test results of each example and comparative example

[0041] As shown in Table 1, all Examples 1 - 4 passed the five performance tests, showing excellent comprehensive performance. In contrast, Comparative Example 1 failed the boiling water resistance and stain resistance tests; Comparative Example 2 did not meet the qualified standard in terms of acid and alkali resistance and stain resistance. This indicates that the comprehensive performance of the examples provided by the present invention is significantly better than that of the comparative examples.

[0042] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for preparing magnetically absorbing glass, characterized in that, Includes the following steps: S1. Glass pretreatment; S2, Glass-sealed bottom; S3, Substrate pretreatment; S4. Electrolyte preparation and electrodeposition: The electrolyte includes magnetic metal salt, complexing agent and dispersant. Electrodeposition is performed on the substrate using a three-electrode system to obtain a magnetic thin film. S5. Post-processing: Heat treatment and surface modification of the magnetic thin film; S6. Adhede the magnetic film: Adhere the magnetic film to the glass backing; S7 and MI processes: using textured molds and micro-nano imprinting technology.

2. The method for preparing magnetically absorbing glass according to claim 1, characterized in that, In step S6, the magnetic thin film is a CoPtMo ternary alloy magnetic thin film.

3. The method for preparing magnetically absorbing glass according to claim 2, characterized in that, In step S4, the electrolyte comprises cobalt sulfate, chloroplatinic acid, and sodium molybdate, wherein the molar ratio of cobalt sulfate, chloroplatinic acid, and sodium molybdate is 2.5–5:1:0.1–2.

4. The method for preparing magnetically absorbing glass according to claim 3, characterized in that, The electrolyte also includes citric acid and polyethylene glycol, wherein the concentration of citric acid is 0.1–0.5 mol / L and the concentration of polyethylene glycol is 0.01–0.1 g / L.

5. The method for preparing magnetically absorbing glass according to claim 1 or 2, characterized in that, In the three-electrode system, the working electrode is made of copper foil; the reference electrode is made of silver / silver chloride electrode. The auxiliary electrode is a platinum sheet.

6. The method for preparing magnetic glass according to claim 1 or 2, characterized in that, In step S4, the pH value of the electrolyte is 4–6; the current density for electrodeposition is controlled to be 1–100 mA / cm². 2 The temperature is 20–60℃; the thickness of the electrodeposited film is controlled to be 50–5000 nm.

7. The method for preparing magnetic glass according to claim 1 or 2, characterized in that, In step S5, the heat treatment specifically includes the following processes: (1) Annealing heat treatment: control the annealing heat treatment temperature to be 400-800℃, the annealing heat treatment time to be 1-3h, and the heating rate to be 1-10℃ / min; (2) Atmosphere-controlled heat treatment: Heat treatment is carried out in an inert and / or reducing atmosphere, with the heat treatment temperature controlled at 400-800℃, the time at 0.5-4h, and the heating rate at 1-10℃ / min; the atmosphere is 5%-10% H2 and 90%-95% Ar by volume, and the gas flow rate is 50-200 mL / min.

8. The method for preparing magnetic glass according to claim 1 or 2, characterized in that, In step S1, the glass pretreatment includes glass faceting and glass cleaning; the glass faceting is done by using a tin lamp to face the glass with the air side facing upwards; the glass cleaning is done by placing the glass with the air side facing upwards in a cleaning machine for cleaning; in step S2, a screen printing process is used to seal the air side of the glass, followed by thermal curing; the screen printing mesh count is 100 or 200, the thermal curing temperature is 180℃, and the thermal curing time is 6–10 min; in step S3, the substrate is selected from metal substrates, semiconductor substrates, or flexible substrates; the substrate pretreatment involves chemical etching, plasma treatment, or ion implantation; in step S5, the surface modification involves depositing SiO2 or Al2O3 on the surface of the magnetic thin film using chemical plating or physical vapor deposition; in step S6, a shadowless adhesive is used to bond the magnetic thin film using an imprinting device, controlling the imprinting device speed to be 3–5 m / min and the energy to be 1000–2000 mJ / cm². 2 .

9. A magnetic glass, characterized in that, It is prepared by any one of the preparation methods according to claims 1 to 8.

10. The application of the magnetic glass according to claim 9 in the fields of home appliance glass panels and smart interactive terminals.

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